CN103172773B - A kind of preparation method of voltalef - Google Patents
A kind of preparation method of voltalef Download PDFInfo
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- CN103172773B CN103172773B CN201110440614.8A CN201110440614A CN103172773B CN 103172773 B CN103172773 B CN 103172773B CN 201110440614 A CN201110440614 A CN 201110440614A CN 103172773 B CN103172773 B CN 103172773B
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Abstract
The present invention relates to a kind of preparation method of daiflon (PCTFE) of high temperature resistant degraded.Adopt suspension polymerization, take deionized water as medium, inorganic peroxide initiator is adopted to cause trifluorochloroethylene (CTFE) polymerization in the presence of a reducing agent, temperature of reaction 20 ~ 80 DEG C, reaction pressure 0.4 ~ 1.5MPa, obtain voltalef powder through filtration, washing and oven dry, then use F
2/ N
2gas mixture carries out fluoridizing termination process, obtains the daiflon of high temperature resistant degraded.This resin has good processability, variable color of not degrading under the processing temperature of 300 DEG C.
Description
Technical field
The present invention relates to the preparation of daiflon, specifically a kind of can the preparation method of voltalef of high temperature resistant degraded.
Background technology
(repeating unit is-CF to voltalef (PCTFE)
2-CFCl-) be the thermoplastic fluorocarbon resin being developed as suitability for industrialized production, excellent performance the earliest, it has outstanding lower temperature resistance, good light transmission, unreactiveness, high physical strength and toughness, extremely low water-vapor permeance.Voltalef not embrittlement in liquid nitrogen, liquid oxygen, natural gas liquids, not creep, the corrosion of ability strong acid, highly basic and strong oxidizer, be a kind of can the special engineering plastics of life-time service in the presence of a harsh environment.
PCTFE is by CTFE (CF
2cFCl) monomer is obtained by free radical initiation, UV initiation or γ-ray-initiated polymerization in solution, suspension or emulsification system.In the ripe preparation method of current PCTFE, all adopt the initiator of non-fluorine, the PCTFE end group obtained is non-fluorine end-group structure, and the structure of non-fluorine end group is stable not, easily degrade to when 240 ~ 280 DEG C in processing temperature, product colour is caused to turn to be yellow, even blackening, degradation.
How improving PCTFE performance, overcome the shortcoming of easy high temperature degradation, is the difficult problem that industry makes great efforts to solve always.US Patent No. 2751376, US2863916, US2902477, US3045000 chlorine or ozone etc. process the end group of PCTFE, can improve the resistance toheat of PCTFE, but due to the impact of side reaction, do not reach desirable object.Patent CN 102020737 adopts cobaltous fluoride to carry out termination process to PCTFE, achieves good effect.But after end-blocking cobaltous fluoride how from PCTFE removing be a larger difficult problem.
Summary of the invention
A preparation method of the PCTFE of high temperature resistant degraded take deionized water as medium, adopts inorganic peroxide initiator in the presence of a reducing agent, CTFE polymerization is caused, after reaction for some time, after filtration under certain temperature and certain pressure, washing, oven dry obtain PCTFE, then use F
2/ N
2gas mixture fluoridizes termination process to PCTFE.
Concrete technology method is as follows:
Add the deionized water that specific conductivity is less than 1 μ in a kettle., add CTFE monomer with after the air in the emptying still of vacuum pump, m (deionization): m (CTFE)=2 ~ 10: 1.Be warmed up to 20 ~ 80 DEG C, add the reductive agent and peroxide initiator that are dissolved in deionized water respectively, m (reductive agent and initiator): (CTFE)=0.01 ~ 0.5: 100.Temperature of reaction preferably 30 ~ 40 DEG C, reaction pressure 0.5 ~ 0.8MPa, the reaction times is 10 ~ 12 hours.Reaction product after filtration, washing, dry, obtain white powder PCTFE.
PCTFE powder is joined in fluoridation device and carries out fluoridation.Fluoridizing device is converter type reactor, adopts flange connect between body of heater and transmission shaft, and blind flange is provided with gas in/out mouth and thermowell, heating unit adopts electric mantle, when converter is rotated, electric mantle maintains static, and gas in/out mouth is closed and disconnected with other pipeline.After PCTFE powder loads converter, deoxygenation of finding time under room temperature, after filling nitrogen, start heating, when material temperature reaches design temperature, deoxygenation of again finding time, then, passes into F
2/ N
2gas mixture, F
2/ N
2in gas mixture, m (F
2): m (N
2)=0.1 ~ 1: 1.Pass into F
2amount is: m (F
2): m (PCTFE) 0.1 ~ 1: 100.After passing into reactant gases, close gas port rapidly and cut off turnover air pipe, opening rotation motor.Fluorination reaction temperature is: 160 ~ 200 DEG C, and the reaction times is 2 ~ 4 hours.After reaction terminates, stop heating and rotate, connecting gas entry/exit pipeline, absorb fluorinated tail gas by NaOH solution, use N
2repeatedly purge, until substantially floride-free in stove, micro-F
2with the inspection of 5wt%KI solution (if containing micro-fluorine gas in gas, KI solution is by flavescence look and even black).After basic floride-free in stove and material cools down, get final product discharging, obtaining can the PCTFE of high temperature resistant degraded.
The invention has the advantages that and adopt F
2/ N
2gas mixture carries out termination process as fluorizating agent to the PCTFE prepared with redox initiation system, and flaorination process is simple, after carrying out termination process, obtains the PCTFE of high temperature resistant degraded, the PCTFE obtained does not degrade under the processing temperature of 300 DEG C, nondiscoloration.The PCTFE obtained compared with traditional method has and applies widely.
Embodiment
Embodiment 1.
At 5L with in the stainless steel polymerization reaction kettle stirred, add the deionized water 3000g that specific conductivity is 0.8 μ, after air in the emptying still of vacuum pump, be filled with CTFE (trifluorochloroethylene) monomer 800g, open and stir, reactor is warmed up to 33 DEG C, adds containing 4g Na with feeder
2s
2o
5aqueous solution 50ml, then to add containing 8g K
2s
2o
8aqueous solution 50ml, keep temperature 37 DEG C, pressure 0.72MPa, react 12 hours, still internal pressure is down to normal pressure, opens kettle cover, PCTFE powder and water is taken out, and after filtration after washing, drying, obtains 670g powder.
Product in table 1, illustrates that product is the homopolymer PCTFE of trifluorochloroethylene through Fourier infrared spectrum measurement result.
Table 1 embodiment 1 non-end-blocking product Infrared spectroscopy data
| Wave number/cm -1 | ％T | |
| 702.33 | 78.937 | |
| 734.66 | 72.843 | |
| 742.91 | 74.508 | |
| 756.48 | 78.859 | |
| 821.01 | 80.344 | |
| 837.82 | 80.178 | |
| 969.59 | 9.923 | C-Cl absorption peak |
| 1124.99 | 20.504 | -CF 2-charateristic avsorption band |
| 1193.71 | 31.520 | -CF 2-charateristic avsorption band |
| 1286.27 | 78.972 | C-F charateristic avsorption band |
Get 200gPCTFE powder wherein, join in the fluoridation still of 1L, deoxygenation of finding time under room temperature, after filling nitrogen, start heating, when temperature in the kettle reaches 170 DEG C, again find time, then, add the F prepared in advance
2/ N
2gas mixture 5.9g (F in this gas mixture
2content is 32.8%wt).After being filled with reactant gases, closing gas port rapidly and cut off admission passage, opening rotation motor.Keep fluorination reaction temperature 170 DEG C, 4 hours reaction times.After reaction terminates, stop heating and rotate, connecting gas entry/exit pipeline, absorb fluorinated tail gas by NaOH solution, use N
2repeatedly purge, micro-fluorine gas 5%wtKI solution inspection (if containing micro-fluorine gas in gas, KI solution is by flavescence look and even black).After basic floride-free in stove and material cools down, get final product discharging.Product measures through Fourier infrared spectrum and obtains the results are shown in Table 2, illustrates that product is the homopolymer PCTFE of trifluorochloroethylene, gets final product the PCTFE of high temperature resistant degraded.
The Infrared spectroscopy data of product after table 2 embodiment 1 end-blocking
| Wave number/cm -1 | ％T | |
| 727.54 | 89.347 | |
| 967.84 | 11.038 | C-Cl absorption peak |
| 1124.06 | 9.972 | -CF 2-charateristic avsorption band |
| 1193.98 | 25.460 | -CF 2-charateristic avsorption band |
| 1284.70 | 77.161 | C-F charateristic avsorption band |
| 1585.51 | 92.300 |
The PCTFE fluoridized before and after end-blocking is done the zero strength time (Z.S.T), degradation property and high temperature color and luster change test, test result is in table 3.
Embodiment 2.
At 5L with in the stainless steel polymerization reaction kettle stirred, add the deionized water 3000g that specific conductivity is 0.5 μ, after air in the emptying still of vacuum pump, be filled with CTFE monomer 600g, open and stir, reactor is warmed up to 30 DEG C, adds containing 1g Na with feeder
2s
2o
5aqueous solution 50ml, then to add containing 1g (NH
4)
2s
2o
8aqueous solution 50ml, keep temperature 30 DEG C, pressure 0.56MPa, react 10 hours, still internal pressure is down to normal pressure, opens kettle cover, PCTFE powder and water is taken out, and after filtration after washing, drying, obtains 512gPCTFE powder.
Get 200gPCTFE powder wherein, join in the fluoridation still of 1L, deoxygenation of finding time under room temperature, after filling nitrogen, start heating, when temperature in the kettle reaches 180 DEG C, again find time, then, add the F prepared in advance
2/ N
2gas mixture 3.5g (F in this gas mixture
2content is 45.5%wt).After being filled with reactant gases, closing gas port rapidly and cut off admission passage, opening rotation motor.Keep fluorination reaction temperature 180 DEG C, 2 hours reaction times.After reaction terminates, stop heating and rotate, connecting gas entry/exit pipeline, absorb fluorinated tail gas by NaOH solution, use N
2repeatedly purge, micro-fluorine gas 5%wt KI solution inspection (if containing micro-fluorine gas in gas, KI solution is by flavescence look and even black).After basic floride-free in stove and material cools down, get final product discharging, obtaining can the PCTFE of high temperature resistant degraded.Product measures through Fourier infrared spectrum, and product is the homopolymer PCTFE of trifluorochloroethylene.
The PCTFE fluoridized before and after end-blocking is done the zero strength time (Z.S.T), degradation property and high temperature color and luster change test, test result is in table 3.
Embodiment 3.
At 5L with in the stainless steel polymerization reaction kettle stirred, add the deionized water 2500g that specific conductivity is 0.5 μ, after air in the emptying still of vacuum pump, be filled with CTFE monomer 350g, open and stir, reactor is warmed up to 33 DEG C, adds containing 0.2g Na with feeder
2s
2o
5aqueous solution 50ml, then to add containing 0.5g (NH
4)
2s
2o
8aqueous solution 50ml, keep temperature 33 DEG C, pressure 0.62MPa, react 10 hours, still internal pressure is down to normal pressure, opens kettle cover, PCTFE powder and water is taken out, and after filtration after washing, drying, obtains 258gPCTFE powder.
Get 100gPCTFE powder wherein, join in the fluoridation still of 1L, deoxygenation of finding time under room temperature, after filling nitrogen, start heating, when temperature in the kettle reaches 200 DEG C, again find time, then, add the F prepared in advance
2/ N
2gas mixture 2.2g (F in this gas mixture
2content is 10.6%wt).After being filled with reactant gases, closing gas port rapidly and cut off admission passage, opening rotation motor.Keep fluorination reaction temperature 200 DEG C, 3 hours reaction times.After reaction terminates, stop heating and rotate, connecting gas entry/exit pipeline, absorb fluorinated tail gas by NaOH solution, use N
2repeatedly purge, micro-fluorine gas 5wt%KI solution inspection (if containing micro-fluorine gas in gas, KI solution is by flavescence look and even black).After basic floride-free in stove and material cools down, get final product discharging, obtaining can the PCTFE of high temperature resistant degraded.Product measures through Fourier infrared spectrum, and product is the homopolymer PCTFE of trifluorochloroethylene.
The PCTFE fluoridized before and after end-blocking is done the zero strength time (Z.S.T), degradation property and high temperature color and luster change test, test result is in table 3.
Daiflon the performance test results prepared by table 3. embodiment of the present invention
Zero strength time (Z.S.T) tests: undertaken by U.S.'s ASTM D 1430-03 standard.
Degradation property is tested: Z.S.T test piece after 5 hours, is tested the mass loss of test piece 270 ± 1 DEG C of heating.
High temperature color and luster change test: Z.S.T test piece after 5 hours, is observed Plaque Color change 300 DEG C of heating.
Claims (2)
1. the preparation method of a voltalef, it is characterized in that: take deionized water as medium, adopt inorganic peroxide initiator in the presence of a reducing agent, cause trifluorochloroethylene (CTFE) polymerization, after reaction, after filtration, washing, oven dry obtain voltalef (PCTFE) resin, then use F
2/ N
2gas mixture fluoridizes termination process to daiflon;
Described termination process concrete technology of fluoridizing is: after PCTFE powder loads converter, deoxygenation of finding time under room temperature, and after filling nitrogen, start heating, when material temperature reaches design temperature, deoxygenation of again finding time, then, passes into F
2/ N
2gas mixture, F
2/ N
2in gas mixture, m (F
2): m (N
2)=0.1 ~ 1:1; Pass into F
2amount is: m (F
2): m (PCTFE)=0.1 ~ 1:100; After passing into reactant gases, close gas port rapidly and cut off turnover air pipe, opening rotation motor; Fluorination reaction temperature is: 160 ~ 200 DEG C, and the reaction times is 2 ~ 4 hours; After reaction terminates, stop heating and rotate, connecting gas entry/exit pipeline, absorb fluorinated tail gas by NaOH solution, use N
2repeatedly purge, until substantially floride-free in stove, micro-F
2with the inspection of 5wt%KI solution, after basic floride-free in stove and material cools down, get final product discharging, obtaining can the PCTFE of high temperature resistant degraded;
The temperature of trifluorochloroethylene polyreaction is 30 ~ 37 DEG C, and polymerization pressure is 0.5 ~ 0.8MPa, and the reaction times is 10 ~ 12 hours;
Described inorganic peroxide initiator is (NH
4)
2s
2o
8or K
2s
2o
8, quality consumption is: m (initiator): m (CTFE)=0.05 ~ 1:100;
Described reductive agent is Na
2s
2o
5, quality consumption is: m (Na
2s
2o
5): m (CTFE)=0.05 ~ 0.5:100;
Use F
2/ N
2gas mixture to the temperature of reaction that PCTFE fluoridizes termination process is: 160 ~ 200 DEG C, and the reaction times is 2 ~ 4 hours.
2. preparation method according to claim 1, is characterized in that: raw material adds quality and is: m (deionized water): m (CTFE)=2 ~ 10:1.
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|---|---|---|---|
| CN201110440614.8A CN103172773B (en) | 2011-12-23 | 2011-12-23 | A kind of preparation method of voltalef |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110440614.8A CN103172773B (en) | 2011-12-23 | 2011-12-23 | A kind of preparation method of voltalef |
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|---|---|
| CN103172773A CN103172773A (en) | 2013-06-26 |
| CN103172773B true CN103172773B (en) | 2015-09-30 |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2569524A (en) * | 1949-06-16 | 1951-10-02 | Du Pont | Polymerization of trifluorochloroethylene in the presence of silver ion, bisulfite ion and persulfate |
| US2689241A (en) * | 1951-03-02 | 1954-09-14 | Kellogg M W Co | Polymerization of fluorine-containing monomers in aqueous redox system |
| US2783219A (en) * | 1953-06-11 | 1957-02-26 | Kellogg M W Co | Manufacture of fluorine containing polymers |
| US2820026A (en) * | 1953-06-11 | 1958-01-14 | Minnesota Mining & Mfg | Manufacture of fluorine containing polymers |
| EP0093580A2 (en) * | 1982-05-03 | 1983-11-09 | Occidental Chemical Corporation | Chlorotrifluoroethylene telomerization process |
| EP0140385A2 (en) * | 1983-11-02 | 1985-05-08 | Occidental Chemical Corporation | Chlorotrifluoroethylene telomerization process |
| EP0438395B1 (en) * | 1988-05-31 | 1995-05-10 | E.I. Du Pont De Nemours And Company | Process for the stabilization of fluoropolymers |
| EP1256591A1 (en) * | 2001-05-07 | 2002-11-13 | Ausimont S.p.A. | Amorphous (per)fluorinated polymers |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05170811A (en) * | 1991-12-25 | 1993-07-09 | Daikin Ind Ltd | Improvement of heat resistance of chlorotrifluoroethylene polymer |
-
2011
- 2011-12-23 CN CN201110440614.8A patent/CN103172773B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2569524A (en) * | 1949-06-16 | 1951-10-02 | Du Pont | Polymerization of trifluorochloroethylene in the presence of silver ion, bisulfite ion and persulfate |
| US2689241A (en) * | 1951-03-02 | 1954-09-14 | Kellogg M W Co | Polymerization of fluorine-containing monomers in aqueous redox system |
| US2783219A (en) * | 1953-06-11 | 1957-02-26 | Kellogg M W Co | Manufacture of fluorine containing polymers |
| US2820026A (en) * | 1953-06-11 | 1958-01-14 | Minnesota Mining & Mfg | Manufacture of fluorine containing polymers |
| EP0093580A2 (en) * | 1982-05-03 | 1983-11-09 | Occidental Chemical Corporation | Chlorotrifluoroethylene telomerization process |
| EP0140385A2 (en) * | 1983-11-02 | 1985-05-08 | Occidental Chemical Corporation | Chlorotrifluoroethylene telomerization process |
| EP0438395B1 (en) * | 1988-05-31 | 1995-05-10 | E.I. Du Pont De Nemours And Company | Process for the stabilization of fluoropolymers |
| EP1256591A1 (en) * | 2001-05-07 | 2002-11-13 | Ausimont S.p.A. | Amorphous (per)fluorinated polymers |
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|---|---|
| CN103172773A (en) | 2013-06-26 |
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Effective date of registration: 20200416 Address after: 030006, No. 467, Jianshe South Road, Xiaodian District, Shanxi, Taiyuan, 2 Patentee after: TAIYUAN DACHENG ENVIRONMENTAL ENERGY CHEMICAL TECHNOLOGY Co.,Ltd. Address before: 116036, No. 7, Ying Sheng Road, Ying Cheng Industrial Park, Ganjingzi District, Liaoning, Dalian Patentee before: CHIA TAI ENERGY MATERIALS (DALIAN) Co.,Ltd. |
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